EP0572254B1 - Harzzusammensetzung und Beschichtungszusammensetzung diese enthaltend - Google Patents

Harzzusammensetzung und Beschichtungszusammensetzung diese enthaltend Download PDF

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EP0572254B1
EP0572254B1 EP93304129A EP93304129A EP0572254B1 EP 0572254 B1 EP0572254 B1 EP 0572254B1 EP 93304129 A EP93304129 A EP 93304129A EP 93304129 A EP93304129 A EP 93304129A EP 0572254 B1 EP0572254 B1 EP 0572254B1
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weight
group
polymer
resin composition
coating
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French (fr)
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EP0572254A3 (de
EP0572254A2 (de
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Yoshitaka Okude
Tsuneyoshi Hisa
Akira Fushimi
Kazuhiko Takeoka
Seigo Miyazoe
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Nippon Paint Co Ltd
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Nippon Paint Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups

Definitions

  • the present invention relates to a thermosetting resin composition which is suitable for top-coating paint and coil-coating paint.
  • Top coating paint for automobiles generally contains, as a film-forming binder, a combination of a hydroxyl group-containing polymer and a melamine curing agent.
  • the cured film obtained from the melamine curing system however, has poor acid resistance and is damaged by acid rain which has recently become one of serious problems. The damage of the film provides poor appearance.
  • the present inventors have proposed novel coating compositions without the melamine curing agent in Japanese Kokai Publications 45577/1990 and 287650/1991.
  • the proposed coating composition cures by means of the reaction of acid and epoxy and therefore has good acid-resistance.
  • degree of crosslinking is set high enough to impart good weather resistance to the cured film, the resulting film has poor elongation and is stiff and brittle.
  • the stiff and brittle film has poor mar resistance and is easily damaged by scratch. It is therefore difficult for the proposed coating compositions to employ as top-coating paint. It is desired to develop top-coating paint which has not only excellent acid resistance but also high mar resistance, water-repellency and good stain resistance.
  • thermosetting resin composition which provides cured film having not only excellent acid resistance but also good weather-resistance, good mar resistance and high water-repellency.
  • the present invention thus provides a thermosetting resin composition comprising:
  • the fluorinated polymer (a) is a copolymer of fluorinated ethylenically unsaturatedd monomers and other copolymerizable ethylenically unsaturated monomers.
  • R 1 represents an alkyl or alkyloyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms.
  • R 2 represents a linear or branched alkylene group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms.
  • R 3 represents a hydrogen atom or -CO-R 6 -COOH in which R 6 is an residue of a dibasic acid anhydride, including an alkenylene, alkylene and cycloalkylene group having 2 to 8 carbon atoms.
  • Typical examples of the ether-containing monomers are cyclohexyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and the like.
  • Typical examples of the ester-containing monomers are vinyl acetate, vinyl propionate, vinyl pivalate, vinyl caprorate and vinyl versatate.
  • Typical examples of the hydroxyl-containing monomers are hydroxyethyl vinyl ether, hydroxypropyl vinyl ether and hydroxybutyl vinyl ether.
  • the acid functionality can be introduced by reacting the hydroxyl group in the above monomer with a dibasic acid anhydride.
  • Examples of the dibasic acid anhydrides are maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, phthalic anhydride and the like.
  • the fluorinated polymer (a) of the present invention may be prepared by copolymerizing the above mentioned monomers, for example 15 to 60 % by weight of the fluorinated monomers, 0 to 30 % by weight ether or ester-containing monomers and the balance of hydroxyl or acid-containing monomers, % by weight being based on total monomer weight.
  • the acid functionality may be introduced either before copolymerizing or after forming a copolymer.
  • the copolymerization may be conducted in a solution, preferably at 40 to 150 °C under elevated pressure in the presence of a polymerization initiator (e.g. azo initiator or peroxides).
  • a polymerization initiator e.g. azo initiator or peroxides.
  • the process for copolymerization is known to the art, for example explained in detail in Japanese Kokai Publications 34207/1982, 286733/1990 and 302411/1990.
  • the fluorinated polymer (a) preferably has a number average molecular weight of 500 to 10,000, more preferably 2,000 to 4,500. Number average molecular weights of less than 500 deteriorate crosslinkability due to less functionality in one polymer molecule, and those of more than 10,000 deteriorate compatibility with the other resins. The molecular weight is determined by Gel Permeation Chromatography (GPC).
  • the fluorinated polymer (a) preferably has a hydroxyl value of 20 to 150 mg KOH/g, more preferably 60 to 120 mg KOH/g, and an acid value of 60 to 180 mg KOH/g, more preferably 80 to 140 mg KOH/g. Hydroxyl values of more than 150 mg KOH/g deteriorate compatibility and those of less than 20 mg KOH/g result in poor water resistance. Acid values of less than 60 mg KOH/g deteriorate crosslinkability and those of less than 180 mg KOH/g result in poor water resistance due to the presence of unreacted acid groups.
  • the fluorinated polymer (a) may be produced as mentioned above, but may be commercially available in the tradename of Lumi-F on from Asahi Glass Co., Ltd.
  • the polymer (b) used in the present invention has both a carboxyl group and a carboxylic ester, and is prepared by copolymerizing 15 to 40 % by weight, preferably 15 to 30 % by weight, of ethylenically unsaturatedd monomers having an acid hydride group and 0 to 85 % by weight of other copolymerizable ethylenically unsaturatedd monomer to obtain a polymer having acid anhydride groups which are then reacted with a hydroxyl compound having 1 to 12 carbon atoms.
  • the ethylenically unsaturated acid anhydrides are itaconic anhydride, maleic anhydride, citraconic anhydride and the like.
  • the other copolymerizable unsaturatedd monomers are those which do not adversely affect on acid hydride group, including styrenes, such as styrene and ⁇ -methylstyrene; (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-, i- or t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and lauryl (meth)acrylate; VeoVa-9® or VeoVa-10® available from Shell Chemical Co.; and the like.
  • the monomers can be used in combination, in order to enhance compatibility with other resins.
  • the other ethylenically unsaturatedd monomers are a combination of styrene and the other monomers.
  • the styrene may be used in an amount of 5 to 40 % by weight based on the total n onomer weight.
  • the copolymerization may be conducted in a solution, for example at a temperature of 100 to 150 °C for 3 to 8 hours in the presence of a radical initiator (e.g. peroxides).
  • the polymer (b) preferably has a number average molecular weight of 500 to 20,000, more preferably 1,500 to 10,000. Number average molecular weights of more than 20,000 elevate polymer viscosity and make it difficult to obtain a coating composition having a high solid content. Those of less than 500 reduce crosslinkability.
  • the polymer thus obtained has average at least two acid anhydride groups in one molecule, preferably average 2 to 15 acid anhydride groups in one molecule. If the acid anhydride groups is average less than 2, the resulting resin composition have poor curing ability.
  • the polymer having acid anhydride groups is then reacted with a hydroxyl compound in a molar ratio of acid anhydride group to hydroxyl group of 1/1 to 1/1.5 to produce a polymer (b) having both hydroxyl group and carboxylic ester group.
  • the hydroxyl compound employed in the present invention is low molecular weight and generally has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms.
  • the half-esterified acid anhydride group will be ring-closed upon curing the composition, but the low molecular weight hydroxyl compound ensures high reproducibility of the ring-closed acid anhydride groups.
  • hydroxyl compounds are methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, dimethylaminoethanol, diethylaminoethanol, acethol, allyl alcohol, propargyl alcohol and the like. Preferred are acethol, allyl alcohol, propargyl alcohol and methanol.
  • the polymer (c) employed in the present invention has both a hydroxyl group and an epoxy group.
  • the polymer (c) preferably has average 2 to 10 epoxy groups, more preferably average 3 to 8 epoxy groups, and average 2 to 12 hydroxyl groups, preferably average 4 to 10 hydroxyl groups. It is preferred that the polymer (c) has an epoxy equivalent of 100 to 800, desirably 200 to 600, and a hydroxyl equivalent of 200 to 1,200, desirably 400 to 1,000. Epoxy equivalents of more than 800 reduce curing ability and those of less than 100 make the cured resin composition hard and brittle. Hydroxyl equivalents of less than 200 deteriorate water resistance and those of more than 1,200 reduce curing ability.
  • the polymer (c) is prepared by copolymerizing
  • the copolymerization may be conducted by art-known methods, for example radical solution polymerization. It is generally conducted at a temperature of 100 to 150 °C for 3 to 8 hours in the presence of a radical initiator (e.g. azo compounds and peroxides).
  • the radical initiator can be used in an amount of 3 to 15 % by weight based on the total monomer weight.
  • an additive such as chain transfer agent may added.
  • the polymer (c) has a number average molecular weight of 500 to 20,000, preferably 1,500 to 10,000.
  • Typical examples of the monomers (i) are 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Praccel FM-1 (a ring-open adduct of ⁇ -caprolactone and 2-hydroxyethyl methacrylate available from Daicel Chemical Industries, Ltd.) and the like.
  • Typical examples of the monomers (ii) are glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate and the like.
  • the monomer (iii) are the same as the other copolymerizable ethylenically unsaturatedd monomer as explained in the polymer having acid anhydride groups.
  • thermosetting resin composition of the present invention is prepared by mixing the above mentioned three polymers (a), (b) and (c).
  • the composition may be made in such an amount ratio that a molar ratio of total acid group in the polymer (a) and the polymer (b) / epoxy group in the polymer (c) is within the range of 1/0.6 to 1/1.2, preferably 1/0.8 to 1/1.0. If the molar ratio is less than 1/0.6, the cured coating has poor crosslinkability. If it is more than 1/1.2, the cured coating easily becomes yellowished.
  • the composition may also be made in such an amount ratio that a molar ratio of total hydroxyl group in the polymers (a) and (c) / acid group in the polymer (b) is within the range of 1/2 to 2/1. If the amount ratio is less than 1/2, the resulting coating has poor mar resistance. It is more than 2/1, the resulting coating has poor water resistance due to the presence of excess hydroxyl groups.
  • thermosetting resin composition of the present invention contains 0.5 to 40 % by weight of the polymer (a), 10 to 60 % by weight of the polymer (b) and 30 to 60 % by weight of the polymer (c).
  • the carboxyl groups and the carboxylic ester groups in the polymer (b) are ring-closed upon heating to form acid anhydride groups which are then reacted with the hydroxyl groups present in the polymers (a) and (c) to form crosslinked bonds and to reproduce acid groups.
  • the reproduced acid groups in the polymer (b) and the acid groups present in the polymer (a) are reacted with the epoxy groups present in the polymer (c) to form crosslinked bonds.
  • the three polymers (a), (b) and (c) are crosslinked together and proceed curing.
  • the low molecular weight compounds which have been reacted with the acid anhydride groups are removed by evaporation upon heating.
  • the thermosetting resin composition of the present invention may further contain a curing catalyst for promoting the reaction between acid and epoxy.
  • a curing catalyst for promoting the reaction between acid and epoxy.
  • the curing catalysts are quaternary ammonium salts, such as benzyltriethylammonium chloride or bromide, tetrabutylammonium chloride or bromide, tetrabutylammonium salicylate or glycolate; sulfonates, such as p-toluenesulfonate; and the like.
  • the curing catalyst may be present in the resin composition in an amount of 0.4 to 2.0 % bt weight based on the solid content of the resin composition.
  • the curing catalyst may be combined with organic tin catalysts which are art-known (see Japanese Kokai Publications 151651/1990 and 279713/1990).
  • organic tin catalysts which are art-known (see Japanese Kokai Publications 151651/1990 and 279713/1990).
  • the tin catalysts are dimethyltin bis(methyl maleate), dimethyltin bis(ethyl maleate), dimethyltin bis(butyl maleate), dibutyltin bis(butyl maleate), SCAT-28® and SCAT-2L® (available from Sankyo Yuki Gosei K.K.), and the like.
  • An amout ratio of curing catalyst/tin catalyst may be within the range of 1/0.2 to 1/4.
  • the resin composition may also contain melamine-formaldehyde resin, in order to enhance crosslinking density and water resistance.
  • a UV absorber commercially available from Ciba Geigy A.G. as Tinubin-900® and a hindered amind light stabilizer available from Sankyo Co., Ltd. as Sanol LS-292 may be added to enhance weather resistance.
  • the composition may also contain other additives, such as rheology controlling agent (e.g. microgel), surface controlling agent.
  • a diluent e.g. alcohols, such as methanol, ethanol, propanol and butanol; hydrocarbon; esters
  • a diluent e.g. alcohols, such as methanol, ethanol, propanol and butanol; hydrocarbon; esters
  • the resin composition has carboxyl groups which are neutralized with amine to make the composition water-dispersible or water-soluble.
  • the resin composition may be formed into aqueous resin composition.
  • the thermosetting resin composition of the present invention is suitably used for a clear coating composition.
  • the clear coating composition is generally applied on a base coating layer formed from a base coating composition which is either aqueous or solvent-borne and contains color pigment. It is also preferred that the clear coating composition is applied on the base coating layer without curing the base coating layer and then the composite layer is baked to cure (two-coat one-bake curing system). In case where the aqueous base coating composition is employed in the two-coat one-bake system, the base coating layer, if necessary, is heated at 60 to 100 °C for 2 to 10 minutes before coating the clear coating composition.
  • the base coating composition is generally explained in U.S. Patents 5,151,125 and 5,183,504. Especially, the aqueous coating composition disclosed in U.S. Patent 5,183,504 is suitable in view of finish appearance and film performance.
  • the composition of the present invention may also contain pigment and can be used as enamel paint.
  • the thermosetting resin composition of the present invention may be modified with a hydroxyalkylamine (e.g. dimethylaminoethanol) to incorporate an amino group into the polymer backbone. It imparts excellent pigment dispersibility to the resin composition.
  • any one which is art-known is employed, for example color pigments, such as iron oxide, lead oxide, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, cadmium yellow, cadmium red and chromium yellow; metallic pigments, such as aluminum flake; organic pigments, such as phthalocyanine blue, Cinquacia red; mica, such as pearl mica; and the like.
  • the pigment content of the composition is usually expressed as pigment-to-resin ratio in solid content. In the practice of the present invention, the pigment-to-resin ratio is as high as 2 : 1, typically within the range of 1 : 0.05 to 1 : 1.
  • thermosetting resin composition may be prepared by art-known methods, for example as enamel paint mixing ingredients by kneader or roll.
  • the resin composition may be applied on a substrate by spraying, brushing, dipping, roll coating, flow coating and the like.
  • the substrate can be any one, including wood, metal, glass, fabric, plastics, plastic foam and the like. Preferred are plastics and metal (e.g. steel and aluminum).
  • the substrate may be primered or intercoated by art-known methods if necessary.
  • the coated coating layer is generally cured by heating at a temperature of 100 to 180 °C, preferably 120 to 160 °C. Curing time may be varied by curing temperature, but generally for 10 to 30 minutes at a temperature of 120 to 160 °C.
  • the film thickness of the resulting coating layer may be varied depending upon its usage, but in many cases within the range of 0.5 to 3 mil.
  • Fluorinated polymers F-i to F-v having the physical data as shown in Table 1 were ordered to companies which handle fluorinated copolymers (i.e. Dikin Industries, Ltd. and Asahi Glass Co., Ltd., both in Japan). The obtained polymers were probably prepared as generally described in Japanese Kokai Publications 54469/1988, 9274/1989 and 158015/1989.
  • the resulting fluorinated polymers were reacted with hexahydrophthalic anhydride (HHPA) in the amounts shown in Table 2 at 140 °C for 0.5 hour to obtain the fluorinated polymers having hydroxyl group and/or acid group A-I to A-V.
  • HHPA hexahydrophthalic anhydride
  • the acid values and non-volatile contents of the resulting polymer are also shown in Table 2.
  • a 2 liter reaction vessel equipped with a thermometer, a stirrer, a condenser, a nitrogen-gas inlet and a dropping funnel, was charged with 250 parts by weight of xylene and 200 parts by weight of a solvent (available from Exxon Co., as Solvesso, and heated to 130 °C.
  • a solvent available from Exxon Co., as Solvesso, and heated to 130 °C.
  • the polymer B-I was yellowish varnish which had a non-volatile content of 50 %, and had an acid value of 114 and a number average molecular weight of 3,000 (GPC).
  • a reaction vessel was charged with 800 parts by weight of butyl acetate and heated to 125 °C.
  • a resin composition was prepared by mixing the following ingredients: Ingredients Parts by weight Polymer A-I 30.0 Polymer B-I 100.0 Polymer C-I 83.4 Tetrabutylammonium salicylate 0.67 Tinubin®-900 2.2 Sanol LS-299 1.1
  • the resulting composition was diluted with a solvent mixture of Solvesso 100/xylene (1/1) to a coatable viscosity to obtain a clear coating composition.
  • a phosphated steel panel was intercoated with Power Top U-30 (electrodeposition paint available from Nippon Paint Co., Ltd.) and Orga P-2 (intercoating paint available from Nippon Paint Co., Ltd.). It was then base-coated with a metallic base paint (Super Lack M-90 available from Nippon Paint Co., Ltd.) and then coated with the above obtained clear coating composition with wet-on-wet. It was baked at 140 °C for 30 minutes. The resulting cured film was evaluated as follow and the results are shown in Table 4.
  • Example 1 A phosphated steel panel was intercoated as described in Example 1, and spray-coated with each of the above mentioned three base coating composition. After pre-heating at 60 °C for 5 minutes, it was coated with the clear coating composition obtained in Example 1 and then cured at 140 °C for 30 minutes. The same evaluations as Example 1 were conducted and the results are shown in Table 4.
  • the clear coating composition of the present invention has excellent acid resistance, mar resistance and water repellency.

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Claims (5)

  1. Wärmehärtende Harzzusammensetzung, umfassend
    (a) 0,5 bis 40 Gew.% eines fluorierten Polymers mit einer Hydroxylgruppe und/oder einer Säuregruppe, dargestellt durch:
    Figure imgb0011
     worin R1 eine lineare oder verzweigte Alkylgruppe oder eine Alkyloylgruppe mit 2 bis 10 Kohlenstoffatomen ist, R2 eine Alkylengruppe mit 2 bis 10 Kohlenstoffatomen ist, R3 ein Wasserstoffatom oder -CO-R6-COOH ist, worin R6 ein Rest eines zweibasischen Säureanhydrids ist, X ein Wasserstoffatom, ein Chloratom oder Fluoratom ist, a, b und c ganze Zahlen sind, die die Gleichung a ≤ b + c erfüllen,
    (b) 10 bis 60 Gew.% eines Polymers mit einer Carboxylgruppe und einem Carbonsäureester, hergestellt durch Copolymerisieren von 15 bis 40 Gew.% eines ethylenisch ungesättigten Monomers mit einer Säureanhydridgruppe und 60 bis 85 Gew.% eines anderen, ethylenisch ungesättigten, copolymerisierbaren Monomers, unter Erhalt eines Polymers mit Säureanhyridgruppen, die dann mit einer Hydroxylverbindung mit 1 bis 12 Kohlenstoffatomen in einem molaren Verhältnis der Säureanhydridgruppen zu den Hydroxylgruppen von 1/1 bis 1/1,5 reagiert werden; worin sich die Angabe der Monomere in Gew.% auf das Gesamtmonomergewicht bezieht; und
    (c) 30 bis 60 Gew.% eines Polymers mit einer Hydroxylgruppe und einer Epoxygruppe, hergestellt durch Copolymerisation von
    (i) 5 bis 40 Gew.% eines Hydroxyalkyl(meth)acrylates, dargestellt durch
    Figure imgb0012
     worin R ein Wasserstoffatom oder eine Methylgruppe ist und n eine ganze Zahl von 2 bis 8 ist,
    (ii) 10 bis 60 Gew.% eines epoxygruppenhaltigen, ethylenisch ungesättigten Monomers, und
    (iii) 0 bis 85 Gew.% eines anderen copolymerisierbaren, ethylenisch ungesättigten Monomers; wobei die Angabe in Gew.% sich auf das gesamte Monomergewicht beziehen.
  2. Wärmehärtende Harzzusammensetzung nach Anspurch 1, die weiterhin (d) ein quartäres Ammoniumsalz als Katalysator enthält.
  3. Wärmehärtende Harzzusammensetzung nach Anspruch 1, die weiterhin (d) eine organische Zinnverbindung als Cokatalysator enthält.
  4. Beschichtungszusammensetzung, umfassend als filmbildende Komponente die wärmehärtende Zusammensetzung nach einem der Ansprüche 1 bis 3.
  5. Verfahren zur Bildung einer Beschichtung auf einem Substrat, umfassend das Beschichten einer in Wasser oder einem Lösungsmittel getragenen Farbbasisfarbe auf ein Substrat mit einer Grundschicht oder einer Zwischenschicht, Beschichten einer klaren Farbe ohne Härten der Basisfarbschicht und anschließendes Backen sowohl der Basisschicht als auch der klaren Beschichtungsschicht zum Härten; wobei die Verbesserung darin besteht, daß die klare Farbe die Beschichtungszusammenstzung nach Anspruch 4 enthält.
EP93304129A 1992-05-27 1993-05-27 Harzzusammensetzung und Beschichtungszusammensetzung diese enthaltend Expired - Lifetime EP0572254B1 (de)

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JP134826/92 1992-05-27
JP13482692 1992-05-27

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EP0572254A2 EP0572254A2 (de) 1993-12-01
EP0572254A3 EP0572254A3 (de) 1995-04-26
EP0572254B1 true EP0572254B1 (de) 1997-07-30

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Publication number Priority date Publication date Assignee Title
EP0702709B1 (de) * 1993-05-14 1998-01-28 E.I. Du Pont De Nemours And Company Anhydrid-epoxy überzugszusammensetzung, modifiziert mit einem fluorpolymer
FR2735781B1 (fr) * 1995-06-23 1997-10-31 Atochem Elf Sa Composition auto-reticulable a base de copolymeres fluores et de copolymeres acryliques, son procede de preparation et son utilisation pour le revetement de substrats

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JP2787326B2 (ja) * 1989-03-03 1998-08-13 関西ペイント株式会社 硬化性組成物
DE59105748D1 (de) * 1990-02-06 1995-07-27 Ciba Geigy Ag Lichtstabilisierte Bindemittel für Lacke.
JPH0819315B2 (ja) * 1990-04-05 1996-02-28 日本ペイント株式会社 熱硬化性樹脂組成物
US5229461A (en) * 1990-05-22 1993-07-20 Daikin Industries, Ltd. Vinylidene fluoride copolymer and composition containing the same

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CA2096994C (en) 2000-01-11
DE69312580D1 (de) 1997-09-04
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EP0572254A3 (de) 1995-04-26
EP0572254A2 (de) 1993-12-01
CA2096994A1 (en) 1993-11-28

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